CN114989407A - Polycarbonate-polysiloxane copolymer, method for producing same, and polycarbonate resin composition containing same - Google Patents
Polycarbonate-polysiloxane copolymer, method for producing same, and polycarbonate resin composition containing same Download PDFInfo
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- CN114989407A CN114989407A CN202210656664.8A CN202210656664A CN114989407A CN 114989407 A CN114989407 A CN 114989407A CN 202210656664 A CN202210656664 A CN 202210656664A CN 114989407 A CN114989407 A CN 114989407A
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- polycarbonate
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- carbon atoms
- polysiloxane
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 18
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 4
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 50
- 239000004417 polycarbonate Substances 0.000 claims abstract description 50
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 13
- 239000000839 emulsion Substances 0.000 claims abstract description 10
- 230000007423 decrease Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 88
- 125000004432 carbon atom Chemical group C* 0.000 claims description 60
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 56
- 125000003118 aryl group Chemical group 0.000 claims description 35
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 35
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 229920001577 copolymer Polymers 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- -1 polysiloxane Polymers 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 22
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 18
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 125000000732 arylene group Chemical group 0.000 claims description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 11
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 10
- 125000002723 alicyclic group Chemical group 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 6
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 claims description 6
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 claims description 6
- 150000001263 acyl chlorides Chemical group 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000006082 mold release agent Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- PTFIPECGHSYQNR-UHFFFAOYSA-N 3-Pentadecylphenol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 3
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 3
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 239000002216 antistatic agent Substances 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229940117389 dichlorobenzene Drugs 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 150000008282 halocarbons Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 3
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 claims description 3
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 125000001174 sulfone group Chemical group 0.000 claims description 3
- 125000003375 sulfoxide group Chemical group 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical group C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 10
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 5
- 239000005770 Eugenol Substances 0.000 description 5
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 5
- 229960002217 eugenol Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical group OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- WGMBWDBRVAKMOO-UHFFFAOYSA-L disodium;4-[2-(4-oxidophenyl)propan-2-yl]phenolate Chemical compound [Na+].[Na+].C=1C=C([O-])C=CC=1C(C)(C)C1=CC=C([O-])C=C1 WGMBWDBRVAKMOO-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 description 1
- 239000004262 Ethyl gallate Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
- C08G64/186—Block or graft polymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention relates to a polycarbonate-polysiloxane copolymer, a method for producing the same, and a polycarbonate resin composition containing the same, wherein a polycarbonate-polysiloxane copolymer main chain comprises a structural unit represented by formula (I) and a structural unit represented by formula (II), the polycarbonate-polysiloxane copolymer increases the yellowness (YI value) of a product after heat resistance at 320 ℃ for 10min by less than 0.9, decreases the weight average molecular weight by less than 300g/mol, and has a total nitrogen residue of less than 10ppb in the polycarbonate-polysiloxane copolymer. According to the polycarbonate-polysiloxane copolymer, a polymerization reaction liquid is dispersed into an emulsion with the particle size of 5-40 micrometers, so that the polycarbonate-polysiloxane copolymer can quickly react to reach a polymerization end point without adding any catalyst. Polycarbonate resin Using the polysiloxane-polycarbonate copolymer of the present inventionThe composition has excellent ageing resistance, chemical resistance and low-temperature impact resistance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polycarbonate-polysiloxane copolymer, a preparation method and a polycarbonate resin composition containing the same.
Background
Polycarbonate (PC) is a high molecular polymer containing carbonate bonds in molecular chains, and can be divided into aliphatic, alicyclic, aliphatic-aromatic and aromatic polycarbonates, wherein the aromatic polycarbonate has excellent mechanical properties, heat resistance, impact toughness, electrical insulation and light transmission, low creep resistance and water absorption, good dimensional stability, excellent dielectric properties and the like, can be used as a thermoplastic engineering plastic, and can be widely applied to the fields of automobiles, electronic equipment, buildings, office supplies, optical discs, sports equipment, medical care, computers, aerospace and the like. However, common PC also has certain defects, such as poor solvent resistance, easy occurrence of stress cracking after touching a solvent, poor impact performance at low temperature, limitation of application in low temperature places, and the like, and needs to be modified in order to widen the application field thereof.
It is known that the low-temperature impact resistance, chemical resistance and the like of polycarbonate materials can be improved by modifying the polycarbonate materials, such as by adding silicon-based modification and improving the low-temperature impact strength of polycarbonate by blending; the low-temperature resistance of the modified polycarbonate can be improved by copolymerizing polycarbonate and polysiloxane, and compared with the blending modification means, the modified polycarbonate has more reliable and more excellent performance and is remarkable in flame retardance, low-temperature impact resistance, chemical corrosion resistance, aging resistance and the like. Has been widely used for producing products such as consumer electronics cover plates, sheaths, brackets, helmets, new energy vehicles charging piles, charging guns and the like.
In the prior art, as disclosed in patent publications CN201710159031.5, CN202010901449.0, CN202010902096.6, and CN201880084106.0, catalysts, such as known tertiary amines or quaternary ammonium salts, are used in the preparation process of the polycarbonate-polysiloxane copolymer, the copolymer solution is post-treated to obtain a powder of the polycarbonate-polysiloxane copolymer, and the catalyst residue in the powder is at a high level, which results in poor thermal aging resistance of the polymer material and affects the application thereof in specific scenes.
In view of the above, it is desirable to develop a polycarbonate-polysiloxane copolymer having excellent aging resistance and a method for preparing the same, and to develop a resin composition comprising the polycarbonate-polysiloxane copolymer, which has excellent low-temperature impact resistance and chemical resistance and heat aging resistance.
Disclosure of Invention
The present inventors have comprehensively studied the product quality of polycarbonate-polysiloxane copolymer, and found that nitrogen-containing active substances such as catalysts/phase transfer agents (tertiary amines, quaternary ammonium salts, etc.) added in the preparation process of polycarbonate-polysiloxane copolymer cannot be completely removed in the post-treatment washing process of polymer solution, and the presence of nitrogen-containing active substances affects the heat resistance, aging resistance and yellowness (YI value) of the material in the test piece due to the residual nitrogen-containing active substances in the polymer body after devolatilization of the polymer solution, thereby completing the present invention.
An object of the present invention is to provide a polycarbonate-polyorganosiloxane copolymer having excellent heat resistance and aging resistance when the total nitrogen residue and the like satisfy certain requirements.
It is still another object of the present invention to provide a method for preparing such a polycarbonate-polyorganosiloxane copolymer.
It is still another object of the present invention to provide a polycarbonate resin composition containing such a polycarbonate-polyorganosiloxane copolymer, which has excellent aging resistance, chemical resistance and low-temperature impact resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polycarbonate-polysiloxane copolymer comprising a polycarbonate structural unit represented by formula (I) and a polysiloxane structural unit represented by formula (II), wherein the polycarbonate-polysiloxane copolymer has less than 10ppb of total nitrogen remaining therein, and the yellowness YI value of the copolymer increases by less than 0.9 after heat resistance at 320 ℃ for 10min, and the weight average molecular weight decreases by less than 300 g/mol; preferably, the mass percentage content of the polysiloxane block part is 15-70%; more preferably, the molded product of the copolymer having a thickness of 3mm has a haze of 70% or more as measured in accordance with ASTM D1003,
wherein R is 1 And R 2 Each independently represents hydrogen, halogen, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 4 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms; a and b each independently represent an integer of 0 to 4; x represents a single bond, an ether bond, a carbonyl group, a thioether bond, a sulfone group, a sulfoxide group, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alicyclic group having 6 to 20 carbon atoms, or a group of the formula (i):
wherein R 'and R' are respectively and independently alkyl with 1-20 carbon atoms, cycloalkyl with 4-20 carbon atoms or aryl with 6-20 carbon atoms; or R 'and R' together form a C4-20 alicyclic ring, said C4-20 alicyclic ring optionally substituted with one or more C1-20 alkyl groups, C6-20 aryl groups, C7-21 aralkyl groups, C5-20 cycloalkyl groups, or combinations thereof;
R 3 and R 4 Each independently represents hydrogen, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; y represents a single bond, an aliphatic or aromatic organic residue; n is an average repeating number of the siloxane monomer, and is an integer selected from 20 to 150, preferably 40 to 100.
In a particular embodiment, the structural polycarbonate units of formula (I) are selected from structural units of formula (III) derived from bisphenol A,
in a particular embodiment, the polysiloxane structural units of formula (II) are selected from structural units of formula (IV) derived from polydimethylsiloxanes whose terminal groups are phenolic hydroxyl groups, Y is an organic residue derived from allylphenols or eugenols;
wherein R is connected to a benzene ring 5 The structure (A) represents the residue of said phenol after removal of the hydroxyl group from the phenyl ring, R 5 Represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group; preferably, R 5 The type selection and the position of the phenol correspond to the substituent groups on the phenol benzene ring one by one; wherein p is 0 to 5, preferably 0 to 3; n is an average number of repetitions, and n is an integer of 20 to 150, preferably 40 to 100.
Preferably, the structural unit represented by formula (IV) is derived from any one of allylphenol-polydimethylsiloxane, preferably 2-allylphenol-polydimethylsiloxane, 3-allylphenol-polydimethylsiloxane, 4-allylphenol-polydimethylsiloxane, 2-methoxy-5-allylphenol-polydimethylsiloxane, 2-methoxy-6-allylphenol-polydimethylsiloxane, and more preferably 2-allylphenol-polydimethylsiloxane or 2-methoxy-4-allylphenol-polydimethylsiloxane.
In a particular embodiment, the weight average molecular weight of the copolymer is 20000 to 55000g/mol, preferably 22000 to 35000 g/mol.
In another aspect, a method for preparing the polycarbonate-polysiloxane copolymer comprises the following steps:
1) preparing a monomer solution: preparing a bisphenol A (BPA) sodium phenolate solution, a phosgene solution, a comonomer solution, an end capping reagent solution and an alkali metal hydroxide solution with certain concentration respectively for later use;
2) polymerization reaction: continuously inputting a bisphenol A sodium phenolate solution, a comonomer solution and a phosgene solution into a polymerization reaction system, mixing and exchanging heat of reaction liquid to generate oligomer with a certain molecular weight, mixing the oligomer with an alkali metal hydroxide solution and an end capping agent solution which continuously enter a buffer kettle, dispersing the mixed solution into reaction emulsion with micron-sized particle size, and continuously entering a three-stage polymerization reaction kettle for a certain time to obtain a polycarbonate-polysiloxane copolymer solution;
3) and (3) post-treatment: purifying the copolymer solution prepared in the step 2) and removing the organic solvent to obtain the polycarbonate-polysiloxane copolymer.
In a particular embodiment, the preparation process does not use any catalyst or phase transfer agent; preferably, the mixed solution in the step 2) is dispersed into an emulsion with a particle size of 5-40 micrometers by a particle size disperser, and preferably into an emulsion with a particle size of 10-30 micrometers.
In a specific embodiment, the end-capping agent is selected from at least any one of phenol, p-methylphenol, p-isopropylphenol, p-tert-butylphenol, p-cyanophenol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol, or p-tert-amylphenol, preferably p-tert-butylphenol or p-cumylphenol;
preferably, the alkali metal hydroxide solution is selected from an aqueous solution of potassium hydroxide, sodium hydroxide, lithium hydroxide or cesium hydroxide, preferably an aqueous sodium hydroxide solution;
preferably, the phosgene solution and the comonomer solution are prepared by using an inert organic solvent, wherein the inert organic solvent is a halogenated hydrocarbon solvent, preferably selected from any one of dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, dichloroethylene, chlorobenzene and dichlorobenzene, and more preferably dichloromethane.
In a specific embodiment, the concentration of bisphenol A in the bisphenol A sodium phenolate solution prepared in the step 1) is 150-200 g/L, preferably 160-170 g/L;
the comonomer solution is a solution of an inert organic solvent of a phenol-terminated polysiloxane monomer, and the mass concentration of the comonomer solution is 10-20%, preferably 15%;
the mass concentration of the end-capping reagent solution is 10-20%, preferably 10-15%;
the mass concentration of the alkali metal hydroxide solution is 25-40%, and preferably 30-35%;
preferably, the molar ratio of the bisphenol A to the phosgene in the polymerization reaction system in the step 2) is 1.01-1.3, and preferably 1.1-1.2%;
the addition amount of the alkali metal hydroxide ensures that the pH value in the reaction system is 11-12.5;
the molar ratio of the bisphenol A to the end-capping reagent is 20-40, and preferably 27-30;
the addition amount of the inert organic solvent is such that the solid content of the reaction liquid is 10-30%, preferably 15-20%;
the reaction residence time of the reaction liquid in the buffer kettle and the third-stage polymerization reaction kettle is determined by the absence of acyl chloride groups in the reaction system, and the preferred residence time is 10-60 min, and more preferably 10-40 min.
More preferably, the polysiloxane monomer has a structural formula shown in formula V below,
wherein R is 3 、R 4 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms; y represents a single bond, an aliphatic or aromatic organic residue; n is the average number of repetitions, n is an integer of 20 to 150, preferably 40 to 100; z represents a halogen atom, -R 5 OH、-R 5 -Z’-R 6 -OH、-R 5 COOH、-R 5 NH2, -COOH or-SH, said R 5 Represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group; the R is 6 An arylene group having 6 to 12 ring-forming carbon atoms, wherein Z' represents an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 10 carbon atoms, or a cycloalkylidene group having 5 to 10 carbon atoms; m represents 0 or 1.
In still another aspect, a polycarbonate resin composition comprises the polycarbonate-polysiloxane copolymer or the polycarbonate-polysiloxane copolymer prepared by the method and an optional aromatic polycarbonate, wherein the polycarbonate-polysiloxane copolymer accounts for 5-100% by mass, and the aromatic polycarbonate accounts for 0-95% by mass; preferably, the aromatic polycarbonate is a polycarbonate which does not contain a siloxane component, preferably a bisphenol A type homopolycarbonate prepared by a phosgene interface method or a bisphenol A type homopolycarbonate prepared by a melt transesterification method.
In a preferred embodiment, the polycarbonate resin composition further contains 0 to 5 wt% of at least any one selected from the group consisting of a mold release agent, a flow aid, a heat stabilizer, an antioxidant, a UV absorber, an IR absorber, a flame retardant, an antistatic agent, a dye, a pigment, and a filler, based on the total weight of the polycarbonate-polysiloxane copolymer and the aromatic polycarbonate.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, through research on the polymerization reaction process of the carbonate-polyorganosiloxane copolymer, the polymerization reaction system is an oil-in-water system, the reaction rate of bisphenol A sodium salt and phosgene is very high, namely, the bisphenol A sodium salt can be converted into acyl chloride oligomer by contact, however, the chain growth of the acyl chloride oligomer and the reaction rate of the acyl chloride oligomer and PDMS are very slow, and a catalyst needs to be added into the system in order to obtain a copolymer with high molecular weight.
The invention controls the state of the polymerization reaction liquid, even if the polymerization reaction liquid of a water-in-oil system is converted into emulsion with the particle size of 5-40 microns by a particle size disperser, the reactants can quickly reach the polymerization end point without adding a catalyst in the reaction system.
The polycarbonate-polysiloxane copolymer of the invention has no nitrogen-containing active substance, namely nitrogen element is remained below 10ppb, the copolymer has excellent heat aging resistance, the yellowness (YI value) of a product is increased by less than 0.9 after the product is subjected to heat resistance for 10min at 320 ℃, and the weight average molecular weight is reduced by less than 300 g/mol.
The polycarbonate resin composition containing the polysiloxane-polycarbonate copolymer of the present invention has excellent aging resistance, chemical resistance and low-temperature impact resistance.
Drawings
FIG. 1 is a schematic flow diagram of a method for preparing a polysiloxane-polycarbonate copolymer according to the present invention.
Detailed Description
The following examples further illustrate the method provided by the present invention for better understanding of the technical solutions of the present invention, but the present invention is not limited to the listed examples and also includes any other known modifications within the scope of the claims of the present invention.
As shown in FIG. 1, a method for preparing a polysiloxane-polycarbonate copolymer according to an interfacial phosgene continuous process of the present invention comprises the steps of:
1) preparing a monomer solution:
dissolving bisphenol A in an aqueous solution of alkali metal hydroxide in D-1 to prepare a bisphenol A (BPA) sodium phenolate solution with a certain concentration;
dissolving phosgene in an inert organic solvent, such as dichloromethane, in D-2 to prepare a phosgene solution with a certain concentration;
in D-3, a terminal phenol end-capped polysiloxane monomer is dissolved in an inert organic solvent to prepare a comonomer solution with a certain concentration, such as a common PDMS/dichloromethane solution;
in D-4, dissolving a blocking agent in an inert organic solvent to prepare a blocking agent solution with a certain concentration;
in D-5, an alkali metal hydroxide is dissolved in water to prepare an alkali metal hydroxide solution having a predetermined concentration.
2) Polymerization reaction: continuously inputting a BPA sodium phenolate solution, a PDMS/dichloromethane solution and a phosgene/dichloromethane solution into a polymerization reaction system by adopting an interface phosgene continuous method process, enabling a reaction solution to pass through a mixer M-1 and a heat exchanger E-1 to generate an oligomer with a certain molecular weight, enabling the reaction solution to enter a buffer kettle D-6, enabling the reaction solution in the D-6 to be mixed with an alkali metal hydroxide solution and an end capping agent solution which continuously enter in a pipeline, further dispersing by using a particle size disperser W-1, and enabling the reaction solution to continuously enter three-stage polymerization reaction kettles R-2, R-3 and R-4 to stay for a certain time to obtain a polysiloxane-polycarbonate copolymer solution;
3) and (3) post-treatment: purifying the copolymer solution prepared in the step 2) and removing the organic solvent to obtain the product.
In the preparation process, no catalyst or phase transfer agent is used in the preparation method, and the oligomer solution is dispersed into an emulsion with the particle size of 5-40 micrometers by a particle size disperser, preferably 10-30 micrometers, so that the interface reaction can be carried out, and the polymerization reaction end point can be quickly reached.
The particle size disperser is not particularly limited, and may be sufficient if the particle size of the reaction solution is dispersed to 5 to 40 μm, and examples thereof include a publicly known emulsifying machine of bruker, japan PRIMIX high-speed emulsifying and dispersing machine, a static mixer, a dynamic mixer, and the like, and preferably a japan PRIMIX high-speed emulsifying and dispersing machine. The rotation speed and the dispersion time of the dispersion machine are not particularly limited, and the particle size of the reaction solution to be controlled is preferably controlled, for example, by dispersing 30 seconds at 10000rpm with a PRIMIX emulsifier, or dispersing 5 seconds at 20000rpm with a Brookfield emulsifier.
The end-capping agent is a monohydric phenol such as phenol, p-methylphenol, p-isopropylphenol, p-tert-butylphenol, p-cyanophenol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol, and p-tert-amylphenol, and these monohydric phenols may be used singly or in combination of two or more, preferably p-tert-butylphenol or p-cumylphenol. The mass concentration of the end-capping reagent solution is 10-20%, and preferably 10-15%.
The alkali metal hydroxide solution is selected from aqueous solutions of potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, preferably aqueous sodium hydroxide solution. The mass concentration of the alkali metal hydroxide solution is 25-40%, and preferably 30-35%.
The inert organic solvent is selected from halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, dichloroethylene, chlorobenzene, dichlorobenzene and the like, and is preferably dichloromethane.
The concentration of the bisphenol A sodium phenolate solution is 150-200 g/L, preferably 160-170 g/L.
The polysiloxane solution is a solution of an inert organic solvent of a phenol-terminated polysiloxane monomer, and the mass concentration of the solution is 10-20%, preferably 15%.
When materials of D-1 and D-2 are conveyed, the molar ratio of bisphenol A to phosgene in the system is 1.01-1.3, preferably 1.1-1.2%; when the D-5 medium alkali liquor is conveyed, the pH value in the system is ensured to be 11-12.5; the molar ratio of the bisphenol A to the end-capping reagent is 20-40, and preferably 27-30; the addition amount of the inert organic solvent is such that the solid content of the reaction liquid is 10-30%, preferably 15-20%; the reaction time of the reaction liquid in D-6, R-3, R-4 and R-5 is 10-60 min, preferably 10-40 min.
The structural formula of the polyorganosiloxane monomer is shown as the following formula V,
wherein R is 3 、R 4 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms; y represents a single bond, an aliphatic or aromatic organic residue; n is an average number of repetitions selected from an integer of 20 to 150, preferably 40 to 10An integer of 0; z represents a halogen atom, -R 5 OH、-R 5 -Z’-R 6 -OH、-R 5 COOH、-R 5 NH2, -COOH or-SH, above R 5 Represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group; r is as defined above 6 An arylene group having 6 to 12 ring-forming carbon atoms, wherein Z' represents an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 10 carbon atoms, or a cycloalkylidene group having 5 to 10 carbon atoms; m represents 0 or 1.
The polyorganosiloxane monomer represented by the general formula (v) can be purchased as a commercial product, or can be easily produced by subjecting a phenol having an ethylenically unsaturated carbon-carbon bond (preferably, vinylphenol, allylphenol, eugenol, isopropenylphenol, or the like) and a terminal of a polyorganosiloxane chain having a predetermined degree of polymerization n to a hydrosilylation reaction; the above phenols are more preferably allylphenol or eugenol; in this case, Y in the above formula (II) and formula (v) becomes an organic residue derived from allyl phenol or eugenol.
The addition amount of the siloxane monomer is 15-70% of the total weight of the polymer, preferably 15-50%, and more preferably 18-22%; in D-3, the polymerization degree n of the polyorganosiloxane is 20 to 150, preferably 40 to 100.
In step 3), the post-treatment may be performed by a method conventional in the art, for example: the copolymer emulsion is first oil-water separated, and the oil phase is washed successively with alkali, acid and water successively, and after water washing, the oil phase is eliminated with solvent and crushed and dried to obtain qualified powder.
The polycarbonate-polysiloxane copolymer prepared by the method comprises a polycarbonate structural unit shown as a formula (I) and a polysiloxane structural unit shown as a formula (II), wherein in the polysiloxane-polycarbonate copolymer,
(1) the product of the polycarbonate-polyorganosiloxane copolymer has a yellowness (YI value) increase of less than 0.9 and a weight average molecular weight decrease of less than 300g/mol after heat resistance at 320 ℃ for 10 min;
(2) less than 10ppb total nitrogen remaining in the polycarbonate-polyorganosiloxane copolymer;
(3) the content of the polyorganosiloxane block portion is 15 to 70 mass%;
(4) a molded article having a thickness of 3mm has a haze of 70% or more as measured by ASTM D1003,
in the formula, R 1 And R 2 Each independently represents hydrogen, halogen, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 4 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms; a and b independently represent an integer of 0 to 4; x represents a single bond, an ether bond, a carbonyl group, a thioether bond, a sulfone group, a sulfoxide group, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alicyclic group having 6 to 20 carbon atoms, or a group of the formula (i):
wherein R 'and R' are respectively and independently alkyl with 1-20 carbon atoms, cycloalkyl with 4-20 carbon atoms or aryl with 6-20 carbon atoms; or R 'and R' together form a C4-20 alicyclic ring, said C4-20 alicyclic ring optionally substituted with one or more C1-20 alkyl groups, C6-20 aryl groups, C7-21 aralkyl groups, C5-20 cycloalkyl groups, or combinations thereof;
R 3 and R 4 Each independently represents hydrogen, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; y represents a single bond, an aliphatic or aromatic organic residue; n is an average repeating number of the siloxane monomer, and is an integer selected from 20 to 150, preferably 40 to 100.
The polycarbonate block represented by the formula (I) in the polysiloxane-polycarbonate copolymer described above is preferably a structural unit derived from bisphenol A, i.e., a structure represented by the formula (III);
the polysiloxane block represented by formula (II) in the polysiloxane-polycarbonate copolymer is preferably derived from a structural unit of polydimethylsiloxane, the polydimethylsiloxane end group is a phenolic hydroxyl group, and Y is an organic residue derived from allyl phenol or eugenol, that is, a structure represented by formula (IV);
in the formula (IV), n and R 5 P, etc. are as defined above.
The above-mentioned structural unit derived from polydimethylsiloxane, the structure of the root-terminal phenolic hydroxyl group, is further preferably derived from allylphenol-polydimethylsiloxane, examples thereof include 2-allylphenol-polydimethylsiloxane, 3-allylphenol-polydimethylsiloxane, 4-allylphenol-polydimethylsiloxane, 2-methoxy-5-allylphenol-polydimethylsiloxane, 2-methoxy-6-allylphenol-polydimethylsiloxane, preferably 2-allylphenol-polydimethylsiloxane or 2-methoxy-4-allylphenol-polydimethylsiloxane.
In still another aspect, a polycarbonate resin composition comprising the polysiloxane-polycarbonate copolymer described herein and optionally other aromatic polycarbonates, wherein the polysiloxane-polycarbonate copolymer is 5 to 100% by mass in the composition resin, the other aromatic polycarbonates are 0 to 95% by mass in the composition resin, and the other aromatic polycarbonates mentioned above are polycarbonates containing no siloxane component, such as bisphenol A type homopolycarbonate prepared by the well-known phosgene interface method or bisphenol A type homopolycarbonate prepared by the melt transesterification method, and the like.
The polycarbonate resin composition prepared in the present invention may further contain one, two or more selected from the group consisting of a mold release agent, a flow aid, a heat stabilizer, an antioxidant, a UV absorber, an IR absorber, a flame retardant, an antistatic agent, a dye, a pigment and a filler in an amount of 0 to 5 wt% based on the total amount of the polysiloxane-polycarbonate copolymer and the aromatic polycarbonate.
The invention is illustrated, but not limited, by the following more specific examples.
The analytical evaluation methods referred to in examples or comparative examples are as follows:
(1) the molecular weight is measured by Gel Permeation Chromatography (GPC) method, using a gel permeation chromatograph of Waters 1515, with tetrahydrofuran as solvent, PS as standard sample, temperature of 30 deg.C, and time of 45 min;
(2) the impact properties were measured according to the standard test method for the Izod impact test of plastics, as defined in ASTM D256-1997;
(3) yellowness index was measured according to ASTM E313 standard, test piece size 50 x 10 mm.
(4) The heat resistance test requires that the dried granules are kept for 10min at the temperature of 300 ℃ of an injection molding machine, and the yellowness index and the weight average molecular weight of a heat-resistant test piece are tested.
(5) Haze was measured according to ASTM D1003 standard, test piece size 100 x 3 mm;
(6) and (3) particle size testing: testing by using a laser particle analyzer;
(7) test for solvent resistance
According to ASTM D543, after sun cream (Banan Boat) is applied to a test piece (test piece thickness 3.2mm) for tensile strength test in a 1.0% strain jig, appearance change is observed, and four grades of A (no crack), B (crack), C (severe crack) and D (fracture) are divided according to the weight of crack generation;
(8) siloxane content test
By nuclear magnetic analysis of copolymers 1 The H-NMR spectrum was calculated by comparing the integral ratio of the peak derived from the dihydric phenol (I) with the integral ratio of the peak derived from the hydroxyaryl-terminal polydiorganosiloxane (II).
Comonomers used in the examples
(1) < eugenol-terminated polyorganosiloxane monomer >
Eugenol-terminated PDMS monomers can be prepared by reference to published literature, for example, to the preparation method described in chinese patent CN 201710159031.5.
The preparation method comprises the following steps: octamethylcyclotetrasiloxane (1420g, 4.80mol), tetramethyldisiloxane (40.2g, 0.3mol) and clay catalyst Filtrol 20(23.4g, 1.6 wt%) were added to a reaction vessel equipped with a stirrer and a thermometer and stirred for 40 minutes to homogenize the material mixture, then the reaction system was heated up to 50 ℃ at a rate of 5 ℃/min and stirred at that temperature for 3 hours, and then the temperature of the reaction system was continuously heated up to 120 ℃ at a rate of 5 ℃/min and stirred vigorously at that temperature for 5 hours, after which the clay catalyst was removed by filtration. The material after removal of the clay catalyst was then put into a reaction tank equipped with a stirrer and a thermometer and a mixed solution of eugenol (167.2g, 1.02mol) and karstedt's platinum catalyst (0.67g) was added dropwise at a rate of 20 g/min with stirring, after which the reaction was stirred at a temperature of 80 ℃ for 13 hours. Followed by distillation at 200 ℃ under reduced pressure to 0.2kPa to remove unreacted starting materials, to give eugenol-terminated polysiloxane in a yield of 99%, with a degree of polymerization of PDMS 55 as determined by nuclear magnetic detection, herein defined for convenience as PDMS-55;
other conditions were unchanged, and by varying the amount of tetramethyldisiloxane, a monomer having a degree of polymerization of siloxane of 100 and a monomer having a degree of polymerization of siloxane of 30, which are defined herein as PDMS-100 and PDMS-30 for convenience, were prepared separately.
Preparation of the examples:
(1) preparing a solution: the concentration of BPA is 170 g/L; the concentration of the polydimethylsiloxane monomer solution is 15 percent; the concentration of the p-tert-butylphenol solution is 11 percent; the concentration of the sodium hydroxide solution is 32%; the solid content of the reaction solution was 16%;
(2) carrying out a polymerization reaction: according to the feeding ratio shown in the table, phosgene, BPA sodium phenolate solution, PDMS monomer solution, dichloromethane and sodium hydroxide solution are continuously added into a polymerization reactor R-1, the pH value of the reaction liquid is maintained at 12, the reaction temperature is maintained at 30 ℃, and the reaction of the reaction liquid in R-2-R-4 is carried outThe particle size disperser is Primix disperser made by Japan, model HOMEGENIZING MIXER TM MARKⅡModel 2.5；
(3) And (3) post-treatment: purifying the copolymer solution prepared in the step (2) and removing the organic solvent to obtain the product.
Examples 1-10 the corresponding polycarbonate-polysiloxane copolymers were prepared according to the procedure described above using the raw material usage tables of Table 1.
TABLE 1 raw material tables for examples 1-10
The results of the performance tests on the copolymers prepared in the above examples are shown in table 2 below:
TABLE 2 Performance test data for copolymers prepared in examples 1-10
Composition examples 11 to 20
1000g of the polysiloxane-polycarbonate copolymer powder prepared in examples 1 to 10, respectively,
2277g of 2100 general-purpose PC resin,
2150 general-purpose PC resin 2277g, antioxidant 6g, and mold release agent 9g, mixing thoroughly, extruding and cutting at 280 deg.C with a coblon CTE35 type extruder, and injection molding the obtained particles, and testing low-temperature impact resistance, chemical resistance and aging resistance.
The formulations of examples 11-20 are shown in Table 3 below:
TABLE 3 data Table of polycarbonate resin compositions of examples 11 to 20
The resin compositions of examples 11 to 20 have the test performance data shown in Table 4 below:
TABLE 4 examples 11-20 polycarbonate resin compositions Performance test data
Preparation of comparative example:
the comparative example was prepared by a procedure different from the example in that the particle size disperser was removed and triethylamine catalyst was added before entering reactor R-2.
Comparative examples 1-10 corresponding polycarbonate-polysiloxane copolymers were prepared according to the procedure described above using the raw material tables of Table 5.
TABLE 5 raw material tables of comparative examples 1 to 10
The results of the performance tests on the copolymers prepared in the above respective comparative examples are shown in table 6 below:
TABLE 6 Performance test data for copolymers prepared in comparative examples 1-10
Comparative compositions 11 to 20
1000g of the polysiloxane-polycarbonate copolymer powder prepared in comparative examples 1 to 10, respectively,
2277g of 2100 general-purpose PC resin,
2150 general-purpose PC resin 2277g, antioxidant 6g, and mold release agent 9g, mixing thoroughly, extruding and cutting at 280 deg.C with a coblon CTE35 type extruder, and injection molding the obtained particles, and testing low-temperature impact resistance, chemical resistance and aging resistance.
The formulations of comparative examples 11-20 are shown in Table 7 below:
TABLE 7 data sheet of comparative examples 11 to 20 polycarbonate resin compositions
The resin compositions of comparative examples 11 to 20 had the test performance data shown in Table 8 below:
TABLE 8 comparative examples 11 to 20 polycarbonate resin compositions Performance test data
As can be seen from the comparison of the above data, when the polysiloxane-polycarbonate copolymer prepared by the present invention does not use a catalyst, the total nitrogen residue in the copolymer is at a low level (no detection), the yellowness (YI value) of the product after the polycarbonate-polyorganosiloxane copolymer is heat-resistant at 320 ℃ for 10min is increased by less than 0.9, and the weight average molecular weight is reduced by less than 300, and the polycarbonate resin composition comprising the polysiloxane-polycarbonate copolymer prepared by the present invention has excellent low-temperature impact resistance and chemical and aging resistance.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined by the claims.
Claims (10)
1. A polycarbonate-polysiloxane copolymer comprising a polycarbonate structural unit represented by formula (I) and a polysiloxane structural unit represented by formula (II), wherein the polycarbonate-polysiloxane copolymer has less than 10ppb of total nitrogen remaining therein, and the yellowness YI value of the copolymer increases by less than 0.9 after heat resistance at 320 ℃ for 10min, and the weight average molecular weight decreases by less than 300 g/mol; preferably, the mass percentage content of the polysiloxane block part is 15-70%; more preferably, the molded product of the copolymer having a thickness of 3mm has a haze of 70% or more as measured in accordance with ASTM D1003,
wherein R is 1 And R 2 Each independently represents hydrogen, halogen, alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 4 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms; a and b each independently represent an integer of 0 to 4; x represents a single bond, an ether bond, a carbonyl group, a thioether bond, a sulfone group, a sulfoxide group, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an alicyclic group having 6 to 20 carbon atoms, or a group of the formula (i):
wherein R 'and R' are respectively and independently alkyl with 1-20 carbon atoms, cycloalkyl with 4-20 carbon atoms or aryl with 6-20 carbon atoms; or R 'and R' together form a C4-20 alicyclic ring, said C4-20 alicyclic ring optionally substituted with one or more C1-20 alkyl groups, C6-20 aryl groups, C7-21 aralkyl groups, C5-20 cycloalkyl groups, or combinations thereof;
R 3 and R 4 Each independently represents hydrogen, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; y represents a single bond, and contains aliphatic or aromatic groupsAn organic residue of (a); n is an average repeating number of the siloxane monomer, and is an integer selected from 20 to 150, preferably 40 to 100.
2. The polycarbonate-polysiloxane copolymer of claim 1, wherein the polycarbonate structural units of formula (I) are selected from structural units of formula (III) derived from bisphenol A,
3. the polycarbonate-polysiloxane copolymer according to claim 1 or 2, characterized in that the polysiloxane structural units of formula (II) are selected from structural units of formula (IV) derived from polydimethylsiloxane whose terminal groups are phenolic hydroxyl groups, Y is an organic residue derived from phenols having an ethylenically unsaturated carbon-carbon bond, preferably allylphenols or eugenols;
wherein, R is connected on a benzene ring 5 The structure (A) represents the residue of said phenol after removal of the hydroxyl group from the phenyl ring, R 5 Represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group; preferably, R 5 The type selection and the position of the phenol correspond to the substituent groups on the phenol benzene ring one by one; wherein p is 0 to 5, preferably 0 to 3; n is the average number of repetitions, n is an integer of 20 to 150, preferably 40 to 100;
preferably, the structural unit represented by formula (IV) is derived from allylphenol-polydimethylsiloxane, preferably any of 2-allylphenol-polydimethylsiloxane, 3-allylphenol-polydimethylsiloxane, 4-allylphenol-polydimethylsiloxane, 2-methoxy-5-allylphenol-polydimethylsiloxane, 2-methoxy-6-allylphenol-polydimethylsiloxane, more preferably 2-allylphenol-polydimethylsiloxane or 2-methoxy-4-allylphenol-polydimethylsiloxane.
4. The polycarbonate-polysiloxane copolymer according to claims 1-3, characterized in that the weight average molecular weight of the copolymer is 20000 to 55000g/mol, preferably 22000 to 35000 g/mol.
5. The method of preparing a polycarbonate-polysiloxane copolymer according to any one of claims 1 to 4, comprising the steps of:
1) preparing a monomer solution: respectively preparing a bisphenol A sodium phenolate solution, a phosgene solution, a comonomer solution, an end-capping reagent solution and an alkali metal hydroxide solution with certain concentrations for later use;
2) polymerization reaction: continuously inputting a bisphenol A sodium phenolate solution, a comonomer solution and a phosgene solution into a polymerization reaction system, mixing and exchanging heat of reaction liquid to generate oligomer with a certain molecular weight, mixing the oligomer with an alkali metal hydroxide solution and an end capping agent solution which continuously enter a buffer kettle, dispersing the mixed solution into reaction emulsion with micron-sized particle size, and continuously entering a three-stage polymerization reaction kettle for a certain time to obtain a polycarbonate-polysiloxane copolymer solution;
3) and (3) post-treatment: purifying the copolymer solution prepared in the step 2) and removing the organic solvent to obtain the polycarbonate-polysiloxane copolymer.
6. The method of claim 5, wherein the preparation process does not use any catalyst or phase transfer agent; preferably, the mixed solution in the step 2) is dispersed into an emulsion with a particle size of 5-40 micrometers by a particle size disperser, and preferably into an emulsion with a particle size of 10-30 micrometers.
7. The production method according to claim 5 or 6, wherein the end-capping agent is selected from at least any one of phenol, p-methylphenol, p-isopropylphenol, p-tert-butylphenol, p-cyanophenol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol, or p-tert-amylphenol, preferably p-tert-butylphenol or p-cumylphenol;
preferably, the alkali metal hydroxide solution is selected from an aqueous solution of potassium hydroxide, sodium hydroxide, lithium hydroxide or cesium hydroxide, preferably an aqueous sodium hydroxide solution;
preferably, the phosgene solution and the comonomer solution are prepared by using an inert organic solvent, wherein the inert organic solvent is a halogenated hydrocarbon solvent, preferably selected from any one of dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, dichloroethylene, chlorobenzene and dichlorobenzene, and more preferably dichloromethane.
8. The preparation method according to any one of claims 5 to 7, wherein the concentration of bisphenol A in the bisphenol A sodium phenolate solution prepared in step 1) is 150 to 200g/L, preferably 160 to 170 g/L;
the comonomer solution is a solution of an inert organic solvent of a phenol-terminated polysiloxane monomer, and the mass concentration of the comonomer solution is 10-20%, preferably 15%;
the mass concentration of the end-capping reagent solution is 10-20%, preferably 10-15%;
the mass concentration of the alkali metal hydroxide solution is 25-40%, and preferably 30-35%;
preferably, the molar ratio of bisphenol A to phosgene in the polymerization reaction system in the step 2) is 1.01-1.3, preferably 1.1-1.2%;
the addition amount of the alkali metal hydroxide ensures that the pH value in the reaction system is 11-12.5;
the molar ratio of the bisphenol A to the end-capping reagent is 20-40, and preferably 27-30;
the addition amount of the inert organic solvent is such that the solid content of the reaction liquid is 10-30%, preferably 15-20%;
the reaction residence time of the reaction liquid in the buffer kettle and the third-stage polymerization reaction kettle is determined by the absence of acyl chloride groups in the reaction system, and the preferred residence time is 10-60 min, and more preferably 10-40 min.
More preferably, the polysiloxane monomer has a structural formula shown in formula V below,
wherein R is 3 、R 4 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms; y represents a single bond, an aliphatic or aromatic organic residue; n is the average repetition number of the siloxane monomer, n is 20 to 150, preferably 40 to 100; z represents a halogen atom, -R 5 OH、-R 5 -Z’-R 6 -OH、-R 5 COOH、-R 5 NH2, -COOH or-SH, said R 5 Represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group; the R is 6 An arylene group having 6 to 12 ring-forming carbon atoms, wherein Z' represents an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 10 carbon atoms, or a cycloalkylidene group having 5 to 10 carbon atoms; m represents 0 or 1.
9. A polycarbonate resin composition comprising the polycarbonate-polysiloxane copolymer according to any one of claims 1 to 4 or the polycarbonate-polysiloxane copolymer produced by the method according to any one of claims 5 to 8, and optionally an aromatic polycarbonate, wherein the polycarbonate-polysiloxane copolymer is 5 to 100% by mass, and the aromatic polycarbonate is 0 to 95% by mass; preferably, the aromatic polycarbonate is a polycarbonate which does not contain a siloxane component, preferably a bisphenol A type homopolycarbonate prepared by a phosgene interface method or a bisphenol A type homopolycarbonate prepared by a melt transesterification method.
10. The polycarbonate resin composition according to claim 9, further comprising 0 to 5 wt% of at least any one selected from the group consisting of a mold release agent, a flow aid, a heat stabilizer, an antioxidant, a UV absorber, an IR absorber, a flame retardant, an antistatic agent, a dye, a pigment, and a filler, based on the total weight of the polycarbonate-polysiloxane copolymer and the aromatic polycarbonate.
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